Polowi 'nski Template Polymerization
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Experimental techniques used |
A similar method of hydrolysis was described7 for poly(vinyl alcohol) used as a template. In this case, “T” was -CH2-CH- and, after hydrolysis, poly(vinyl alcohol) and polyacrylic or polymethacrylic acid were obtained. The hydrolyzed product gives the color reaction with I2 in the presence of H3BO3 - specific to poly(vinyl alcohol). The second product of hydrolysis, after esterification by diazomethane, was identified as poly(methyl methacrylate) by NMR and IR spectrometry. Hydrolysis was also applied in the case of ladder-type polymers obtained by polymerization of mutliallyl monomers.26 The polymerization should result in polymer consisting, at least partly, ladder-type blocks:
After hydrolysis by 2N methanol solution of H2SO4, the product was neutralized with KOH to pH=5 and methanol evaporated. The dry residue was expected to be poly(allilamine), polymethacrylic acid, and K2SO4. Indeed, after extraction with anhydrous methanol and acetone, poly(allilamine) was identified by NMR and IR spectrometries. After evaporation, solvent from the methanol part of the extract insoluble in chloroform part was obtained. After esterification by diazomethane the product was identified as poly(methyl methacrylate) on the basis of IR and 1H-NMR spectroscopy. IR spectroscopy was applied in order to examine the copolymerization of multimethacrylate (p-cresyl-formaldehyde oligomers with methacrylic groups) with styrene.5 It was found that double bond peak at 1650 cm-1 disappeared during the process and it was absent in the product of polymerization. Polymerization and
Experimental techniques used |
145 |
Figure 11.7. IR spectra of multimethacrylate (Ia), homopolymer (II), and copolymer (IV). Reprinted from: R. Jantas and S. Polowinski, J. Polym. Sci., Polym. Chem., 24, 1819 (1986).
copolymerization of multimethacrylate obtained by reacting poly(vinyl alcohol) with methacryloyl chloride were also examined by IR spectroscopy.7 Change in the intensity at 1630 cm-1 is illustrated in Figure 11.7.7
Disappearance of absorption band at 1630 cm- 1 was found for the multimethacrylate homopolymer (II) and copolymer (IV) of these two different multimonomers. IR spectra, NMR spectra and hydrolysis experiments lead to the following structures:
for multimethacrylate Ia:
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Experimental techniques used |
for homopolymer II:
and for copolymer:
Application of typical methods such as X-ray diffraction for examination of this class of materials is still to be assessed.
REFERENCES
1.A. Blumstein and S. R. Kakivaya in Polymerization of Organized Systems, Ed. H. G. Elias,
Gordon & Breach Sci. Pub., New York, p. 189, 1977.
2.N. Shavit and J. Cohen in Polymerization of Organized Systems, Ed. H. G. Elias, Gordon & Breach Sci. Pub., New York, p. 213, 1977.
3.J. Ferguson and A. Eboatu, Eur. Polym. J., 25, 721 (1989).
4.V. S. Rajan and J. Ferguson, Eur. Polym. J., 18, 633 (1982); J. Ferguson (private communication).
5.S. Polowinski, Eur. Polym. J., 14, 463 (1978).
6.R. Jantas, J. Szumilewicz, G. Strobin, and S. Polowinski, J. Polym. Sci., Polym. Chem., 32, 295 (1994).
7.R. Jantas and S. Polowinski, J. Polym. Sci., Polym. Chem., 24, 1819 (1986).
8.J. Matuszewska-Czerwik and S. Polowinski, Eur. Polym. J., 27, 743 (1991).
9.J. Matuszewska-Czerwik and S. Polowinski, Eur. Polym. J., 27, 1335 (1991).
10.J. Matuszewska-Czerwik and S. Polowinski, Eur. Polym. J., 28, 1481 (1992).
11.J. Gons, J. Vorenkamp, and G. Challa, J. Polym. Sci., Polym. Chem. Ed., 15, 3031 (1977).
12.J. Matuszewska-Czerwik and S. Polowinski, Makromol. Chem., Rapid Commun., 10, 513 (1989).
13.G. O. R. Alberda van Ekenstein, D. W. Koetsier, and Y. Y. Tan, Eur. Polym. J., 17, 845 (1981).
14.G. O. R. Alberda van Ekenstein and Y. Y. Tan, Eur. Polym. J., 17, 839 (1981).
15.G. O. R. Alberda van Ekenstein and Y. Y. Tan, Eur. Polym. J., 18, 1061 (1982).
Experimental techniques used |
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16.G. O. R. Alberda van Ekenstein, B. J. Held, and Y. Y. Tan, Angew. Makromol. Chem., 131, 117 (1984).
17.J. Ferguson and S. A. O. Shah, Eur. Polym. J., 4, 343 (1968).
18.J. Ferguson and S. A. O. Shah, Eur. Polym. J., 4, 611 (1968).
19.J. Ferguson and C. McLeod, Eur. Polym. J., 10, 1083 (1974).
20.D. V. Subotic, J. Ferguson, and B. C. H. Warren, Eur. Polym. J., 27, 61 (1991).
21.J. Szumilewicz, to be published.
22.A. Blumstein, E. Bellantoni, S. Panrathnam, M. Milas, and Y. R. Ozcayir, IUPAC Symposium Bucharest-Romania, 1983, Mater. Sec. I, 1, p. 277.
23.A. N. Eboatu and J. Ferguson, Nigerian J. Sci. Res., 2, 52 (1989).
24.Abd-Ellatif, Polym. Int., 28, 301 (1992).
25.H. Kämmerer and A. Jung, Makromol. Chem., 101, 284 (1966).
26.R. Jantas and S. Polowinski, J. Polym. Sci., Polym. Chem. Ed., 27, 475 (1989).
|
Subject Index |
149 |
|
Subject Index |
|
activation energy 45, |
enzyme 1 |
oligoradicals 10 |
47, 107, 112 |
equilibrium constants |
orientation 22, 24 |
applications 129 |
15 |
partition coefficient 93 |
association 124 |
experimental |
pendant groups 23 |
atactic 45, 47 |
techniques 133 |
peroxide decomposition |
autoacceleration 34 |
fibrillized structure 123 |
108 |
Boltzmann constant |
glass transition |
photopolymerization |
104 |
temperature 120, 121 |
43, 98 |
catalyzed reaction 1 |
graft copolymer 86 |
polyacids 27, 30, 95 |
chain effect 3 |
growing centers 7 |
polybase ionenes 35 |
chain transfer 85, 86 |
helix structure 5, 23 |
polycomplex 122, 130 |
complexation 45, 121 |
heteropolycondensation |
polycondensation 5, 77, |
complex formation 46 |
|
89 |
conjugated bonds 46 |
6, 7, 8 |
polyelectrolyte 84, 121 |
conversion 43, 102 |
hydrogen bonding 29 |
poly(ethylene oxide) 36 |
copolycondensation 59 |
hydrolysis 30, 75, 144 |
polymeric catalyst 2 |
copolymerization 11, |
inhibitor 42, 43, 103 |
polymerization degree |
13, 59 |
initiation 9 |
38 |
critical chain length 10, |
initiator 23, 27, 31, 32, |
polymerization rate 41, |
|
106 |
42, 93, 95 |
24 |
interaction 19, 22, 24, |
polynucleotides 5 |
critical concentration |
39, 77, 79, 101 |
polypeptide 1, 2 |
109 |
intermolecular reaction |
poly(vinyl pyrrolidone) |
crosslinks 66 |
49 |
36, 45, 79, 99, 107 |
crystal lattice 2 |
isotactic 45 |
post-effect 102 |
cyclic dimers 34 |
kinetics 44, 89, 93, 106, |
precipitation 34 |
daughter polymer 1, |
111 |
probabilities 15, 73, 74 |
24, 31, 43, 84, 141 |
ladder polymers 49, 62, |
propagation 9, 11, 14, |
degradative addition |
115, 119, 143 |
27, 66 |
31, 33, 86 |
Langmuir theory 21 |
protonization 28 |
dialysis 19 |
macroradical 88 |
radical |
dipole-dipole |
maleic acid 39 |
copolymerization 60 |
interaction 48 |
maleic anhydride 46 |
radical lifetime 91 |
dissociation 124 |
Mayo-Lewis equation |
radical polymerization |
donor-acceptor |
15, 70, 71 |
9, 90 |
interaction 74 |
methylation 40 |
rate constants 14, 97 |
DNA 1, 5, 23 |
montmorillonite 2 |
reaction order 29, 92 |
entropy 104, 105, 107 |
multimonomer 10, 51, |
reactivity ratio 64, 71 |
entropy of mixing 104 |
53, 55, 62, 111, 134 |
replication 3 |
150 |
Subject Index |
replication origin 5 |
solvation 19, 20, 24 |
template effect 3 |
resonance 86 |
spacer 24 |
termination 9, 11, 91, |
ring-opening polymeri- |
stereocomplex 124, 125 |
106, 107 |
zation 53, 59, 84, 89 |
steric hindrance 24 |
triads 73 |
secondary reactions 83 |
substrate orientation 19 |
unit average length 71, |
selective sorption 2 |
syndiotactic 30 |
72 |
self-replication 6 |
tacticity 3 |
volume fraction 21, 109 |
sequence distribution |
temperature 34 |
|
16 |
template activity 116 |
|